Detergent-whitener compositions



United States Patent 3,309,319 DETERGENT-WHITENER COMPGSITKONS Todd L.Coward, Cincinnati, Ohio, and Norman R. Smith, Konigshach, Germany,assignors to The Procter & Gamhie Company, Cincinnati, Ohio, acorporation of bio o Drawing. Fiied Sept. 23, 1965, Ser. No. 489,726 It)Claims. (Cl. 252-137) This invention relates to a detergent compositioncomprising a mixture of detergent materials which provide superiorwhitening eifectiveness on nylon for a certain stilbene whitenercompound.

Those compounds which have optical whitening properties when depositedon fabrics are complex and expensive chemicals. Full utilization oftheir advantageous whitening properties requires that they be used indetergent systems from which they are effectively and efiicientlydeposited on the cloth being laundered. blylon is an especiallydifiicult textile material for efiicient whitener deposition. It isdifiicult to predict, among the many different optical whiteningmaterials, those wh ch are susceptible to efi'lcient deposition andthose for wlnch deposition may be improved by any particular detergentformulations.

Accordingly, it is an object of this invention to provide a detergentcomposition especially formulated with a s ecific stilbene opticalwhitener which composition has superior and unexpected characteristicsregarding the whitening of nylon fabric.

This and other objects are achieved with the detergent comprising anorganic anionic synthetic detergent compound and at least one of acertain class of zwitterionic and sernipolar detergent compoundshereinafter more fully described, in a weight ratio range of 4:1 to 1:4,together with a minor amount of a certain stilbene whitener.

The stilbene whitener used in the compositions of this invention is 4,4bis[(4,6-di-anilino-s-triazin-Z-yl)amino]-2,2'-stilbene disulfonate,preferably the disodium salt.

It has the following chemical structure:

H N III i N where M (monovalent salt) is alkali metal, such as sodium orpotassium, or ammonium or triethanolammonium. This optical whitener iswell known per se as a whitener and is available under the trade namesCalcofluor White PG concentrate, Blancophor CN-76, Hiltamine Artic WhiteEP, Tinopal TAS and Cellu-Brite. Hereinafter this will be referred to asstilbene whitener.

This stilbene whitener, when deposited on fabrics such as nylon in anordinary detergent system such as one based on sodium dodecyl benzenesulfonate, is a moderately efficient whitener. It is also moderatelyefiicient when deposited on such fabrics from detergent systems based onsome zwitterionic or semipolar detergent compounds. Quite surprisingly,however, it was found that stilbene whitener provided superior whiteningefficacy when deposited on nylon fabric during laundering with adetergent composition based on a 4:1 to 1:4 by weight mixture of ananionic detergent compound and a zwitter- "ice ionic or semi-polardetergent compound of the sultaine, betaine, amine oxide, phosphineoxide or sulfoxide classes as hereinafter more fullydescribed. It wasfurther surprisingly found that this improved nylon whiteningeffectiveness from this particular mixture of detergent compounds wasapparently unique 'with the stilbene whitener and this surprisingwhitening property was not observed in these detergent mixtures withother conventional optical whitening compounds. No explanation can beoffered for this particular result since the complexities of opticalwhitening compounds per se and their behavior in various detergentsystems and on various fabrics is not subject to any known set ofprinciples. Stilbene whitener provides an optical whitening functioningfor nylon fabric in the detergent systems of this invention superior tothat which results when this same material is deposited from a detergentsystem containing either an anionic detergent compound alone or one ofthe specified zwitterionic or semi-polar detergent compounds alone orfrom some other detergent system such as a nonionic ethoxylate detergentsystem or a cationic detergent system.

The stilbene whitener is used in an amount ranging from about 0.05% toabout 2% of the total Weight of the mixture of anionic detergent andzwitterionic or semipolar detergent.

This ternary mixture, i.e., stilbene whitener+anionic syntheticdetergent-l-zwitterionic or semi-polar detergent, is preferably used inaqueous laundering solution at a weight concentration ranging from about0.05% to about 2%. The washing solution temperature preferably rangesfrom about F. to about F. Under these conditions the whitening effect onnylon fabric is surprisingly superior.

The organic anionic synthetic detergent of this inventron can be any ofthe variety of such detergent compounds which are widely known and used.The selectlon of any particular anionic detergent compound does notappear to be critical, but for their preferred detergencycharacteristics the following anionic detergent compounds are especiallydesirable. The anionic class of organic synthetic detergents can bebroadly described as the water-soluble salts, particularly the alkalimetal salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl radical containing from about 8 to about 22carbon atoms and a radical selected from the group consisting ofsulfonic acid and sulfuric acid ester radicals. Important examples ofthese synthetic detergents are the sodium or potassium alkyl sulfates,especially those obtained by sulfating tallow or coconut oil fattyalcohols; sodium or potassium alkyl benzene sulfonates, in which thealkyl group in a straight or branched chain contains from about 9 toabout 16 carbon atoms; potassium or sodium salts of sulfonated a olefinscontaining from 10 to 18 carbon atoms, especially those described incopending application of Pflaumer et al. Ser. No. 423,364 filed Jan. 4,1965; sodium alkyl glyceryl ether sulfonates, especially those ethers ofthe higher alcohols derived from tallow and coconut oil; sodium coconutoil fatty acid monoglyceride sulfates and sulfonates; sodium orpotassium salts of sulfuric acid esters of the reaction product of onemole of a high er fatty alcohol (e.g., tallow or coconut oil alcohols)and one to five (e.g. three) moles of ethylene oxide; sodium orpotassium salts of sulfated condensation products of one mole of alkylphenol with l to 5 moles ethylene oxide, e.g. those products with anaverage of about four units of ethylene oxide per molecule and in whichthe alkyl radicals contain about 9 carbon atoms; the reac-' tion productof fatty acids esterified with isethionic acid and neutralized withsodium hydroxide where, for example, the fatty acids are derived fromcoconut oil; sodium or potassium salts of fatty acid amide of a methyltaurine in which the fatty acids, for example, are derived from coconutoil; and others known in the art, a number being specifically set forthin United States Letters Patent Numbers 2,486,921, 2,486,922 and2,396,278.

The preferred anionic synthetic detergents in this invention are sodiumdodecyl benzene sulfonate, sodium tallow alkyl sulfate and the sodiumsalt of sulfonated a tetradecene.

The zwitterionic quarternary ammonium compounds which are used in thecompositions of this invention are compounds of the general formulawherein R is an alkyl radical having from about 10 to about 18 carbonatoms, R and R are each alkyl radicals having from about 1 to about 3carbon atoms, R is an alkylene or hydroxyalkylene radical having from 1to 4 carbon atoms, and X is SO= SO= or COO=. R is preferably a propeneor 2-hydroxypropene radical.

Compounds which conform to the above general formula are characterizedby the presence of both positive and negative charges which areinternally neutralized (i.e., zwitterionic). When the anion X is S= orSO= these compounds are referred to as sultaines. The term betaine isemployed when the anion X is COO=. The following structural formulas areillustrative of the two types and their inner salt character.

R2 R2 R NR;S o R NR4C 0 R3 0 R: O

Sultaines Betaines Examples of compounds falling within this definitionare 3-(N,N-dimethyl-N-hexadecylammonio) propane-1- sulfonate and3-(N,N-dlmethyl-N-dodecylammonio) 2- hydroxy propane -l-sulfonate andwhich are especially preferred for their excellent cool water detergencycharacteristics. The most marked improved whitening results in thecomposition and process of this invention are obtained with theanionic-zwitterionic detergent system.

The semi-polar compounds of the compositions of this invention comprisethe amine oxide, phosphine oxide and sulfoxide classes defined asfollows.

Tertiary amine oxides are those corresponding to the following generalformula R R R N+O, wherein R is an alkyl or hydroxyalkyl radical of fromabout to about 18 carbon atoms, and R and R are each methyl, ethyl orhydroxyethyl radicals. R is preferably dodecyl. The arrow in the formulais a conventional representation of a semi-polar bond. Examples of amineoxides suitable for use in this invention include dimethyldodecyl amineoxide, dimethyl-2-hydroxydodecyl amine oxide, dimethyldecyla-mine oxide,dimet-hyltetradecylamine oxide, dimethylhexadecylamine oxide and dodecyldiethanolamine oxide.

Tertiary phosphine oxides are those corresponding to the followinggeneral formula R R R P+O wherein R is an alkyl, aikenyl ormonohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chainlength and R and R are each alkyl or monohydroxyalkyl groups containingfrom 1 to 3 carbon atoms. R is preferably dodecyl. The arrow in theformula is a conventional representation of a semi-polar bond. Examplesof suitable phosphine oxides are:

dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide,

tetradecylmethylethylphosphine oxide, cetyldimethylphosphine oxide,stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide,dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide,dodecyldipropylphosphine oxide, dodecyldi(hydroxymethyl) phosphineoxide, dodecyidi(2-hydroxyethyl) phosphine oxide,tetra-decylmethyl-2-hydroxypropyl phosphine oxide,oleyldimethylphosphine oxide, and 2-hydroxyldodecyldimethylphosphineoxide.

Dialkyl sulfoxides, R R S+O, are those containing one short chain alkyl(R e.g. methyl or ethyl, and one long hydrophobic chain (R which cancontain ether linkages and hydroxy groups and which contain from about10 to about 18 carbon atoms, e.g. alkyl, hydroxyalkyl oralkoxyhydroxyalkyl. R is preferably dodecyl, hydroxydodecyl ordodecoxyhydroxypropyl. Examples include:

octadecyl methyl sulfoxide dodecyl methyl sulfoxide tetradecyl methylsulfoxide 3-methoxytridecyl methyl sulfoxide 3-hydroxytridecyl methylsulfoxide 3-hydroxy-4-do-decoxybutyl methyl sulfoxide In the abovedescribed zwitterionic and semi-Polar compounds the short chain groups,i.e., R R R R R R and R are preferably methyl for greater watersolubility.

The ternary mixture compositions of this invention, i.e., anionicdetergent, zwitterionic or semi-polar detergent and stilbene whitener,are advantageously employed with water-soluble detergency builder saltsto form built laundry detergent compositions, especially for washing andwhiten= ing nylon. Preferably the ratio of ternary mixture to buildersalt ranges from about 1:05 to about 1:10. Ordinarily detergentcompositions employ from about 10% to about 25% of the ternary mixture,from about 20 to about 60% builder, the balance being essentially adiluent such as water or Na SO The pH of such built compositions usuallyranges from about 8 to about 12.

Examples of water-soluble inorganic alkaline detergency builder saltsare alkali metal carbonates, phosphates, polyphosphates, and silicates.Specific examples of such salts are sodium and potassiumtripolyphosp'hates, carbonates, pyrophosphates, phosphates,-andhexametaphosphates.

Examples of organic alkaline sequestrant builder salts are (1) alkalimetal amino polycarboxylates [e.g., sodium and potassium ethylenediaminetetraacetates, N-(2-hydroxyethyl)-ethylene diamine triacetates,nitrilo triacetates, and N-(Z-hydroxyethyl)-nitrilo diacetates]; (2)alkali metal salts of phytic acid (e.g., sodium and potassiumphytates-see US. Patent 2,739,942); (3) Watersoluble salts ofethane-l-hydroxy-l,l-diphosphonate (e.g., the trisodium and tripotassiumsalts) as described in US. Patent 3,159,581; (4) water-soluble salts ofmethylene diphosphonic acid (e.g., trisodium and tripotassium methylenediphosphonate and the other salts described in the copending applicationof Francis L. Diehl, Serial No. 266,025, filed March 18, 1963); (5)water-soluble salts of substituted methylene diphosphonic acids (e.g.,trisodium and tripotassium ethylidene, isopropylidene,benzylmethylidene, and halomethylidene diphosphonates and the othersubstituted methylene diphosphonates disclosed in the copendingapplication of Clarence H. Roy, Serial No. 266,055, filed March 18,1963); (6) water-soluble salts of polycarboxylate polymers andcopolymers as described in the copending application of Francis L.Diehl, Serial No. 269,359, filed April 1, 1963 (e.g., polymers ofitaconic acid; aconitic acid; maleic acid; mesaconic acid; fumaric acid,methylene malonic acid; and cinronic acid and copolymers with themselvesand other compatible monomers such as ethylene).

Mixtures of organic and/or inorganic builders can be used and aregenerally desirable. Especially preferred are the mixtures of buildersdisclosed in the copending application of Burton H. Gedge, Ser. No.398,705, filed Sept. 23, 1964, e.g. ternary mixtures of sodiumtripolyphosphate, sodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,l, diphosphonate.

ther minor ingredients can also be added to the compositions of thisinvention including: soil suspending agents such ascarboxymethylcellulose; other optical brighteners; dye; antibacterialagents; oxygen bleaches; tarnish inhibitors such as benzotriazole. Thetotal amount of these minor ingredients is preferably less than 5 to byweight of the composition. The composition can also contain 2l0% alkalimetal silicate as corrosion inhibitors.

The following examples are given additionally to illustrate the natureof the invention and it will be understood that the invention is notlimited thereto. All parts and percentages are by weight unlessotherwise specified.

EXAMPLE I A series of heavy-duty laundry detergent compositions wereformulated according to the following guide formula:

Percent Organic synthetic detergent 17.5 Sodium tripolyphosphate 50Sodium silicate having SiO :Na O ratio of 1.6:1 6 Moisture 10 Sodiumcarboxymethylcellulose 0.3

Stilbene whitener (as herein before defined) as the sodium salt(disodium salt) 0.2 Sodium sulfate Balance A series of compositions, insets of four each (described in greater detail below), were tested in afourbucket miniature washer with paddle-arm agitators, designed as asimplified, scaled-down Washing machine (similar to a tergotometer butlarger in capacity). Each bucket was filled with one gallon of water at130 F. of 7 grains per gallon hardness. 0.2% by weight of eachcomposition was added to each bucket and the resulting solution wasagitated for one minute. Fabric loads of 12 inch by 12 inch unsoiledcloth swatches (3 terrycloth, 2 muslin and 2 nylon per load) were addedto each washing solution. The fabrics were pretreated to remove anyfiuorescers used in the cloth manufacture. The swatches were washed forten minutes in the respective washer buckets. After washing, water wasextracted from the swatches. The buckets were then emptied of wash waterand filled with one gallon each of rinse water at 100 F. of 7 grains pergallon hardness. The swatches were rinsed for two minutes. Afterrinsing, water was again extracted from the swatches which were thendried in an automatic steam drier.

All the test compositions were rated as poorer or better in nylon fabricwhiteness than each other on a relative basis. Comparisons were made inartificial north daylight by skilled graders who subjectively rated thenylon fabric swatches on the basis of (a) no difference, (b) slightlybetter or poorer, (c) markedly better or poorer or (d) very markedlybetter or poorer, with arbitrary positive numbers indicating betterresults and similar arbitrary negative numbers indicating poorerresults, the numbers conforming to the subjective scale. The graders didnot know which compositions were used to wash the fabrics being graded.The number of washings, evaluations and grades in the test, the designof the tests and the analysis thereof were such to make the results andthe conclusions therefrom statistically significant.

In the series of detergents prepared and tested, the 17.5% activeportion in the above guide formula was varied as to synthetic detergenttype and proportions as follows; the corresponding results in nylonfabric whiteness as determined by panel score units are noted:

Nylon Anionic Zwitterionic or Semi Polar Weight Fabric Ratio whitenessGrade 17.5% TAS. 0% HAPS 1. 15 13.12% 'IAS 4.38% TAS 1. +1.00 0% TAS 6517.5% ABS 25 13.12% ABS. 60 4.38% ABS 80 0% ABS 17.5% HAPS 1. 15

17.5% ABS 0% DDAO 25 13.12% ABS 3:1 10 4.33% ABS 1:3 80 0% ABS 17.5%DDAO 45 17.5% ABS- 0% DDPO 0.00 13.12% ABS. 0. 00 4.38% ABS 60 0% ABS 6017.5% 'IAS 0 .15 13.12% TAS 25 4.38% 'IAS 13.12% HDMSO r 40 0% TAS 17.5%HDMSO 50 17.5% TAS 0% tallow betaine 05 4.38% tallow beta1ne 3:1 1013.12% tallow betaine 1:3 75 17.5 tallow betaiue TAS=sodium tallow alkylsulfate.

HAPS =3-(N,N-dimethyl-N-coconut alkyl ammonio).2-hydroxypropane-l-sulionate (The coconut alkyl was approximately 65%dodecyl 25% tetradecyl 10% hexadecyl).

ABS =sodium dodecylbene sulfonate.

D D A0 dhnethyldodecylamine oxide.

D DP 0 dunethyldodecylphosphine oxide.

HD MSO =methyl-3-dodecoxy-Z-hydroxypropyl sulfoxide.

Tallow betaine=3(N, N,-dimethyl-N tallo\v alkyl ammonio) acetate,

These results show the surprisingly superior whiteness results achieve-dby the process and compositions of this invention. These data showsuperior results with a ratio of 3:1 to 1:3 anionic to switterionic orsulfoxide and with a ratio of 1:3 anionic to amine or phosphine oxide.

This detergent can be used to provide a product washing solutionconcentration of 0.5% in water at F. to launder and whiten nylon fabric.

The ternary mixtures of this invention can be used in the followingdetergent formulations of the type of copending application Serial No.423,008 of January 4, 1965, which are especially useful in cleaning andwhitening nylon, particularly under the washing conditions outlined inExample I:

Unbuilt liquid detergent Percent Sodium salt of sulfonated a tetradecene5 3-(N,N-dimethyl-N-tetradecyl ammonio) propane-1- sulfonate Stilbenewhitener (as defined above-diammonium salt) 0.2 Ethanol 10 Water Balance7 Granular detergent Percent Sodium salt of sulfonated 1:1 mixture of adodecene and a tetradecene l 3-(N,N-dimethyl-N-dodecyl am-monio) 2hydroxy propane-l-sulfonate 10 Stilbene whitener (as defined abovedipotassium salt) 0.3 Sodium tripolyphosphate 20 Sodium nitrilotriacetate10 Trisodium ethane-l-hydroxy 1,1-diphosphonate l0 Moisture 10 Sodiumsilicate 6 Sodium sulfate Balance Other modifications can be made in theinvention without departing from the spirit of it. What is claimed is:

1. A detergent composition, especially suitable for cleaning andwhitening nylon consisting essentially of (1) a mixture of (a) ananionic, non-soap, organic synthetic detergent having in its molecularstructure an alkyl radical containing from 8 to 22 carbon atoms and aradical selected from the group consisting of sulfonic acid and sulfuricacid ester radicals and (b) a detergent selected from the groupconsisting of zwitterionic and semi-polar synthetic detergents and (2)4,4'-bis[4,6-dianilino-s-triazin-2-yl)amino]-2,2'-stilbene disulfonate;wherein: the weight ratio of (a) to (b) ranges from about 3:1 to about1:3 in the case of zwitterionic and sulfoxide semi-polar detergents andis about 1:3 in the case of amine oxide and phosphine oxide semi-polardetergents; the amount by weight of said disulfonate ranges from about0.05% to about 2.0% of the said mixture of (a) and (b); saidzwitterionic detergent has the formula wherein R is an alkyl radicalhaving from 10 to 18 carbon atoms, R and R are each alkyl radicalshaving from 1 to 3 carbon atoms, R; is selected from the groupconsisting of alkylene and hydroxyalkylene radicals having from 1 to 4carbon atoms and X is selected from the group consisting of 80 S0 andCOO=; said semipolar detergent is selected from the group consisting ofamine oxide, phosphine oxide and sulfoxide detergents, said amine oxidehaving the formula wherein R is selected from the group consisting ofalkyl and hydroxyalkyl radicals having from to 18 carbon atoms and R andR7 are each selected from the group consisting of methyl, ethyl andhydroxyethyl radicals, said phosphine oxide having the formula R3R9RmP Owherein R is selected from the group consisting of alkyl,

alkenyl and hydroxyalkyl radicals having from 10 to 18 carbon atoms andR and R are selected from the group consisting of alkyl andmonohydroxyalkyl radicals having 1 to 3 carbon atoms, and said sulfoxidehaving the formula wherein R is selected from the group consisting ofmethyl and ethyl and R is selected from the group consisting of alkyl,hydroxyalkyl and alkoxy radicals having from 10 to 18 carbon atoms.

2. The composition of claim 2 wherein component (b) is a zwitterionicdetergent and component (2) is the disodium salt.

3. The composition of claim 2 wherein component (a) is selected from thegroup consisting of C -C alkyl benzene sulfonates, C C alkyl sulfatesand sulfonated C C a olefin salts.

4. The composition of claim 3 wherein component (b) is3(N,N-dimethyl-N-coconut alkyl ammonio) Z-hydroxypropane-l-sulfonate.

5. The composition of claim 4 wherein component (a) is selected from thegroup consisting of sodium tallow alkyl sulfate, sodium dodecyl benzenesulfonate and sodium tetradecene sulfonate.

6. A built detergent consisting essentially of the composition of claim1 and a water-soluble detergency builder salt in a weight ratio ofcomposition to builder ranging from 1:05 to 1:10, said water solublebuilder salt being selected from the group consisting of inorganicalkaline detergency builder salts and organic alkaline sequestrantbuilder salts.

7. The built detergent of claim 6 wherein the said composition is thatof claim 2.

8. The built detergent of claim 6 wherein the said composition is thatof claim 5.

9. A method of cleaning and whitening nylon com prising the steps ofpreparing an aqueous washing solution of about 0.05% to about 2.0% byweight of the composition of claim 1 and washing nylon fabric therein.

10. The method of claim 9 wherein said composition is that of claim 2and the washing solution temperature ranges from about F. to about F.

References Cited by the Examiner UNITED STATES PATENTS 2,787,595 4/1957Webb 252138 3,213,030 10/1965 Diehl 252152 3,222,287 12/ 1965 Laughlin252152 XR 3,223,647 12/1965 Drew 252--137 FOREIGN PATENTS 1,100,5831/1958 Germany.

LEON D. ROSDOL, Primary Examiner.

S. E. DARDEN, Assistant Examiner.

1. A DETERGENT COMPOSITION, ESPECIALLY SUITABLE FOR CLEANING ANDWHITENING NYLON CONSISTING ESSENTIALLY OF (1) A MIXTURE OF (A) ANANIONIC, NON-SOAP, ORGANIC SYNTHETIC DETERGENT HAVING IN TIS MOLECULARSTRUCTURE AN ALKYL RADICAL CONTAINING FROM 8 TO 22 CARBON ATOMS AND ARADICAL SELECTED FROM THE GROUP CONSISTING OF SULFONIC ACID AND SULFURICACID ESTER RADICALS AND (B) A DETERGENT SELECTED FROM THE GROUPCONSISTING OF ZWITTERIONIC AND SEMI-POLAR SYNTHETIC DETERGENTS AND (2)4,4''-BIS(4,6-DIANILINO-S-TRIAZIN-2-YL)AMINO)-2,2''-STILBENEDISULFONATE; WHEREIN: THE WEIGHT RATIO OF (A) TO (B) RANGES FROM BOUT3:1 TO ABOUT 1:3 IN THE CASE OF ZWITTERIONIC AND SULFOXIDE SEMI-POLARDETERGENTS AND IS ABOUT 1:3 IN THE CASE OF AMINE OXIDE AND PHOSPHINEOXIDE SEMI-POLAR DETERGENTS; THE AMOUNT BY WEIGHT OF SAID DISULFONATERANGES FROM ABOUT 0.05% TO ABOUT 2.0% OF THE SAID MIXTURE OF (A) AND(B); SAID ZWITTERIONIC DETERGENT HAS THE FORMULA